CN103664601A - [6,6]-phenyl-C61-methyl butyrate (PCBM) and fullerene derivative synthesis method - Google Patents
[6,6]-phenyl-C61-methyl butyrate (PCBM) and fullerene derivative synthesis method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
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- C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70
Abstract
The present subject matter relates to methods for the synthesis of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and fullerene derivatives in a yield of at least 40%.
Description
Technical field
Theme of the present invention relates to [6,6]-phenyl-C
61the synthetic method of-methyl-butyrate (PCBM) and fullerene derivate.
Background
At the film organic electronic device for commercial applications, for example obtain great progress aspect the exploitation of photocell, transistor, photodetector, sensor and other devices.Many these devices have utilized the semi-conductor (solution-processable semiconductor) of the solution processable based on purified form fullerene derivate.The most frequently used fullerene derivate is the phenyl-C that classifies as methylene radical soccerballene (methanofullerene)
61-methyl-butyrate (PCBM).
PCMB is from C
60the analogue of [60] PCBM of soccerballene.[70] PCBM is used as semi-conductor in organic electronic industry, be used in particular for polymer solar device (WIENK etc., Angewadte Chemie, 2003, (115), 3493-3497) and transistor (Anthopoulos etc., Journal of Applied Physics, (98), 054503).
The method of preparing in the past PCBM has 35% productive rate (Hummelen etc., J. Org. Chem 1995,60,532) at the most.At Yang etc., Carbon 2007,45, and in 2951 production method, the productive rate of PCBM only has 33.6% at the most.
Because PCBM is widely used as the semi-conductor for the solution processable of film organic electronic device, be therefore starved of higher PCBM productive rate.
General introduction
Theme of the present invention relates to the synthetic method of formula I compound or its steric isomer.In one embodiment, this synthetic method comprises the reaction between soccerballene and formula II compound:
Wherein X is C
nh
2n+1, R is C
nh
2n+1, and n=0-20; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; The molar ratio range that wherein soccerballene and formula II compound exist in reaction is 1:2 to 2:1; Wherein reaction produces the formula I compound of at least 40% productive rate.
In one embodiment, formula I compound is [6,6]-phenyl-C
61-methyl-butyrate (PCBM) or [5,6]-phenyl-C
61-methyl-butyrate (F1-OMe).Its chemical structure shows below respectively.
In another embodiment, theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the first reaction and the second reaction; The first reaction comprises alkaline reagents (basic reagent) and formula II compound to produce diazoalkane; The second reaction comprises that the diazoalkane that the first reaction is produced mixes with soccerballene; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; Its Chinese style II compound and the molar ratio range of alkaline reagents in the first reaction are 1:2 to 2:1; Wherein the first reaction and the second reaction produce the formula I compound of at least 40% productive rate.
In another embodiment, by
oin-dichlorobenzene, heat the synthetic PCBM of F1-OMe.Reaction process is as follows.
Accompanying drawing summary
The chemical structure of Fig. 1 display type I compound.
The chemical structure of Fig. 2 display type II compound.
Fig. 3 shows the chemical structure of F1-OMe.
Fig. 4 shows the chemical structure of PCBM.
Fig. 5 shows the chemical structure of MBT.
Fig. 6 shows the chemical structure of 1-phenyl-1-(3-(methoxycarbonyl) propyl group) diazomethane.
Fig. 7 shows the reaction process of synthetic compound of formula i.
Fig. 8 shows the reaction process of the first reaction of synthetic diazoalkane.
Fig. 9 shows the reaction process of the second reaction of synthetic F1-OMe.
Figure 10 shows from the reaction process of the synthetic PCBM of F1-OMe.
Figure 11 sets forth the figure that comes purifying soccerballene and its derivative by affinity chromatography.
Describe in detail
definition
The implication of all technology used herein and scientific terminology is identical with the implication that theme one skilled in the art of the present invention understand conventionally.For the object of understanding theme of the present invention and building appended Patent right requirement provides following definitions.
Term used herein " diazoalkane " refers to have general formula R
2cN
2any diazo compound, wherein R is hydroxyl or any saturated organic group.
Term used herein " soccerballene " refers to any molecule of the hollow spheres, ellipticity or the tubular form that are comprised of carbon completely.In preferred embodiments, soccerballene used herein can contain 60,70,76,78,84 or 90 carbon atoms.
Term used herein " isomer " refers to the different compounds with same molecular formula, and comprises other isomeric forms of cyclic isomers and circular part.
Term used herein " steric isomer " refers to only distinguishing isomer in the spatial arrangement mode of atom.
Term used herein " a " or " an " comprise odd number and plural number, unless stated otherwise.Therefore, term " a ", " an " or " at least one (kind) " are interchangeably for the application.
In whole application, the description of a plurality of embodiments has been used term " to comprise "; Yet it will be understood by those skilled in the art that in some specific situation, embodiment alternatively use term " substantially by ... form " or " by ... form " describe.
For understanding better the present invention, instruct and never limit the object of teachings, except as otherwise noted, numeral and other numerical value of all expression quantity used herein, percentage ratio or ratio are interpreted as in all cases by term " about " modified.Therefore, unless indicated to the contrary, the approximation of the digital parameters proposing in specification sheets below and appended claim for changing with the required character of attempting to obtain.In any case, each digital parameters should be at least according to the numeral of reported significant digit and apply common rounding-off method and explain.
Other terms used herein with its in the art known implication define.
Theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the reaction between soccerballene and formula II compound:
Wherein X is C
nh
2n+1, R is C
nh
2n+1, and n=0-20; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; The molar ratio range that wherein soccerballene and formula II compound exist in reaction is 1:2 to 2:1; Wherein reaction produces the formula I compound of at least 40% productive rate.
In one embodiment, formula I compound is [6,6]-phenyl-C
61-methyl-butyrate (PCBM) or [5,6]-phenyl-C
61-methyl-butyrate (F1-OMe).Chemical structure shows below respectively.
In such embodiment, formula II compound is tosylhydrazone, for example 4-benzoyl methyl-butyrate
p-tosylhydrazone (methyl 4-benzoylbutryrate
p-tosylhydrazone, MBT).The chemical structure of MBT shows below.
In one embodiment, its Chinese style II compound is that MBT and soccerballene are C
60, reaction process is as follows.
In one embodiment, the mol ratio that soccerballene and formula II compound exist in reaction is preferably 1:1.
Alternative aspects of the inventive subject matter, reaction also produces the by product that is no more than 22% productive rate.
In another embodiment, reaction can be by having pk
athe alkaline reagents of >10 causes.The limiting examples of available alkaline reagents is sodium methylate in this respect.
In another embodiment, theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the reaction between soccerballene and formula II compound:
Wherein X is C
nh
2n+1, R is C
nh
2n+1, and n=0-20; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; Wherein in reaction, use the formula II compound of 0.25 mmol-1.0 mmol; Wherein reaction produces the formula I compound of at least 40% productive rate.
In an embodiment in this respect, in reaction, use the formula II compound of 0.5 mmol.In another embodiment, this reaction also produces the by product that is no more than 22% productive rate.Reaction can be by having pk
athe alkaline reagents of >10 causes.In non-limiting embodiments, alkaline reagents can be sodium methylate.
In another embodiment, theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the reaction between soccerballene and formula II compound:
Wherein X is C
nh
2n+1, R is C
nh
2n+1, and n=0-20; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; Wherein in reaction, use the formula II compound of 0.25 mmol-1.0 mmol; And wherein reaction also produces the by product that is no more than 22% productive rate.
In an embodiment in this respect, in reaction, use the formula II compound of 0.5 mmol.In another embodiment, this reaction produces the formula I compound of at least 40% productive rate.This reaction can be by having pk
athe alkaline reagents of >10 causes.In non-limiting embodiments, alkaline reagents can be sodium methylate.
In another embodiment, theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the reaction between soccerballene and formula II compound:
Wherein X is C
nh
2n+1, R is C
nh
2n+1, and n=0-20; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; The molar ratio range that wherein soccerballene and formula II compound exist in reaction is 1:2 to 2:1; Wherein reaction also produces the by product that is no more than 22% productive rate.
In an embodiment in this respect, the mol ratio that soccerballene and formula II compound exist in reaction is 1:1.In another embodiment, this reaction produces the formula I compound of at least 40% productive rate.This reaction can be by having pk
athe alkaline reagents of >10 causes.In nonrestrictive embodiment, alkaline reagents can be sodium methylate.
In a further embodiment, any above-mentioned method for the synthesis of formula I compound or its steric isomer also comprises purge process, as shown in figure 11.Purge process can be for being selected from one or more in affinity chromatography, reverse-phase chromatography and adsorption chromatography.
Another embodiment of theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the first reaction and the second reaction:
Wherein X is C
nh
2n+1, and n=0-20; The first reaction comprises alkaline reagents and formula II compound with generation diazoalkane:
Wherein R is C
nh
2n+1, and n=0-20; The second reaction comprises that the diazoalkane that the first reaction is produced mixes with soccerballene; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; The molar ratio range that its Chinese style II compound and alkaline reagents exist in the first reaction is 1:2 to 2:1; Wherein the first reaction and the second reaction produce the formula I compound of at least 40% productive rate.
In one embodiment, diazoalkane is 1-phenyl-1-(3-(methoxycarbonyl) propyl group) diazomethane.The chemical structure of 1-phenyl-1-(3-(methoxycarbonyl) propyl group) diazomethane shows below.
Therefore, on the one hand, the first reaction is used MBT to produce 1-phenyl-1-(3-(methoxycarbonyl) propyl group) diazomethane as part starting raw material.Aspect this, the reaction process of the first reaction is as follows.
On the other hand, the second reaction is by 1-phenyl-1-(3-(methoxycarbonyl) propyl group) diazomethane that the first reaction is produced and soccerballene C for example
60mix and produce [5,6] phenyl-methyl-butyrate.Aspect this, the reaction process of the second reaction is as follows.
When the molar ratio range existing in the first reaction when formula II compound and alkaline reagents is 1:2 to 2:1, the F1-OMe of the first reaction and the second reaction generation at least 40% productive rate.
In another embodiment, by
oin-dichlorobenzene, heat F1-OMe and synthesize PCBM.This reaction process shows below.
When the molar ratio range existing in the first reaction when formula II compound and alkaline reagents is 1:2 to 2:1, the PCBM of the first reaction and the second reaction generation 40% productive rate.
In another embodiment, the mol ratio that formula II compound and alkaline reagents exist in the first reaction can be 1:1.
On the other hand, the first reaction and the second reaction produce the by product that is no more than 22% productive rate.
In one embodiment, alkaline reagents has pk
a>10.The limiting examples of this alkaline reagents is sodium methylate.
Another embodiment of theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the first reaction and the second reaction:
Wherein X is C
nh
2n+1, and n=0-20; The first reaction comprises alkaline reagents and formula II compound with generation diazoalkane:
Wherein R is C
nh
2n+1, and n=0-20; The second reaction comprises that the diazoalkane that the first reaction is produced mixes with soccerballene; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; Its Chinese style II compound and the molar ratio range of alkaline reagents in the first reaction are 1:3 to 4:3; Wherein the first reaction and the second reaction produce the formula I compound of at least 40% productive rate.
In an embodiment in this respect, the mol ratio that formula II compound and alkaline reagents exist in the first reaction is 1:1.In another embodiment, the first reaction and the second reaction produce the by product that is no more than 22% productive rate.Alkaline reagents used can have pk
a>10.In non-limiting embodiments, alkaline reagents can be sodium methylate.
Another embodiment of theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the first reaction and the second reaction:
Wherein X is C
nh
2n+1, and n=0-20; The first reaction comprises alkaline reagents and formula II compound with generation diazoalkane:
Wherein R is C
nh
2n+1, and n=0-20; The second reaction comprises that the diazoalkane that the first reaction is produced mixes with soccerballene; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; The molar ratio range that its Chinese style II compound and alkaline reagents exist in the first reaction is 1:3 to 4:3; Wherein the first reaction and the second reaction also produce the by product that is no more than 22% productive rate.
In an embodiment in this respect, the mol ratio that formula II compound and alkaline reagents exist in the first reaction is 1:1.In another embodiment, the first reaction and the second reaction produce the formula I compound of at least 40% productive rate.Alkaline reagents used can have pk
a>10.In nonrestrictive embodiment, alkaline reagents can be sodium methylate.
Another embodiment of theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the first reaction and the second reaction:
Wherein X is C
nh
2n+1, and n=0-20; The first reaction comprises alkaline reagents and formula II compound with generation diazoalkane:
Wherein R is C
nh
2n+1, and n=0-20; The second reaction comprises that the diazoalkane that the first reaction is produced mixes with soccerballene; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; Wherein in the first reaction, use the formula II compound of 0.25 mmol-1.0 mmol; Wherein the first reaction and the second reaction produce the formula I compound of at least 40% productive rate.
In an embodiment in this respect, in the first reaction, use the formula II compound of 0.5 mmol.In another embodiment, the first reaction and the second reaction produce the by product that is no more than 22% productive rate.Alkaline reagents used can have pk
a>10.In nonrestrictive embodiment, alkaline reagents can be sodium methylate.
Another embodiment of theme of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the first reaction and the second reaction:
Wherein X is C
nh
2n+1, and n=0-20; The first reaction comprises alkaline reagents and formula II compound with generation diazoalkane:
Wherein R is C
nh
2n+1, and n=0-20; The second reaction comprises that the diazoalkane that the first reaction is produced mixes with soccerballene; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; Wherein in the first reaction, use the formula II compound of 0.25 mmol-1.0 mmol; Wherein the first reaction and the second reaction also produce the by product that is no more than 22% productive rate.
In an embodiment in this respect, in the first reaction, use the formula II compound of 0.5 mmol.In another embodiment, the first reaction and the second reaction produce the formula I compound of at least 40% productive rate.Alkaline reagents used can have pk
a>10.In nonrestrictive embodiment, alkaline reagents can be sodium methylate.
In another embodiment, any above-mentioned method for the synthesis of formula I compound or its steric isomer also can comprise purge process, as shown in figure 11.Purge process can be and is selected from one or more in affinity chromatography, reverse-phase chromatography and adsorption chromatography.
Another embodiment of the present invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the reaction between diazoalkane and soccerballene:
Wherein X is C
nh
2n+1, and n=0-20; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; Wherein reaction produces the formula I compound of at least 40% productive rate.
In an embodiment in this respect, reaction also produces the by product that is no more than 22% productive rate.
Another embodiment of the invention relates to the synthetic method of formula I compound or its steric isomer, and described method comprises the reaction between diazoalkane and soccerballene:
Wherein X is C
nh
2n+1, and n=0-20; Wherein soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90; And wherein reaction also produces the by product that is no more than 22% productive rate.
In an embodiment in this respect, reaction produces the formula I compound of at least 40% productive rate.
In another embodiment, any above-mentioned method for the synthesis of formula I compound or its steric isomer also can comprise purge process, as shown in figure 11.Purge process can be and is selected from one or more in affinity chromatography, reverse-phase chromatography and adsorption chromatography.
Embodiment
Following examples have proved the various embodiments of theme of the present invention.
Embodiment 1
F1-OMe's is synthetic
By 4-benzoyl methyl-butyrate
p-tosylhydrazone (MBT, 0.5 mmol) and sodium methylate (NaOMe, 0.5 mmol) add in the double-neck flask that 100 mL are dry and vacuumize processes three times (each 15 minutes).Then 10 mL pyridines are injected and provide N
2in the flask of entrance and stir 15 minutes.In the round-bottomed flask of 100 mL, by the C of 0.5 mmol
60be dissolved in 20 mL
o-dichlorobenzene (ODCB).By C
60degassed 15 minutes of solution (with nitrogen bubble), then injects pyridine solution.At N
2under introducing, mixture is stirred 22 hours at 75 ℃.Total reaction flow process as shown in Figure 7.
Embodiment 2
Two steps of F1-OMe are synthetic
Relate to two steps herein synthetic.The first reaction for producing diazonium compound from tosylhydrazone.Pyridine is as solvent.For effectively producing diazonium compound, temperature that need to approximately 70 ℃.The reaction process of the first reaction as shown in Figure 8.
The second reaction is for producing F1-OMe by typical diazonium addition approach.ODCB is as solvent.Once diazonium compound forms, will be rapidly by C
60catch.The second reaction process as shown in Figure 9.
The following institute of transformation efficiency (X), F1-OMe productive rate (Y) and by-product yields (Z) defines:
After reaction, solution is transferred to round-bottomed flask concentrated and by column chromatography purifying in a vacuum.Collection contains unreacted C
60the first flow point (purple), concentrated into about 20 mL and precipitate with ether (120 mL) in a vacuum.By suspension supersound process 1 minute centrifugal.Residue is processed to twice in the same way with ether, and spend the night 70 ℃ of vacuum-dryings.Obtain dry unreacted C
60and can reuse.Productive rate: 136.6 mg(37.95%).The second flow point (brown) that collection contains F1-OMe, and with C
60identical mode is carried out purifying, uses methyl alcohol to replace ether as precipitation agent.Productive rate: 185.8 mg(40.83%).
Embodiment 3
PCBM's is synthetic
185.8 mg F1-OMe are joined in the double-neck flask that 100 mL are dry, and vacuumize processing three times.Stirring adds 30 mL ODCB and is heated to reflux 20 hours.With HPLC, monitor isomerization.Gained brown solution is concentrated into approximately 15 mL in a vacuum, and by precipitating with methyl alcohol described in F1-OMe.With HPLC, analyze end product, purity is calculated as 99.93%.Reaction process as shown in figure 10.
Embodiment 4
By differential responses condition, carry out the synthetic of PCBM
As shown in table 1, with MBT, NaOMe and the C of different amounts
60synthetic PCBM.
Table 1: carry out the synthetic of PCBM by differential responses condition
As highlighted demonstration in table 1, the 5th row has comprised the optimum condition that synthesizes PCBM with at least 40% productive rate.
About the information comprising herein, to the various deviations of theme accurate description of the present invention, for theme person of ordinary skill in the field of the present invention, be apparent, do not depart from the spirit and scope of claim.Theme of the present invention is not considered to be limited in the scope of defined program, feature or component, because preferred embodiment and other descriptions only mean to illustrate the particular aspects of provided theme of the present invention.In fact, for biomechanics or those skilled in the relevant art, be apparently for implementing the various modifications of institute's describing mode of theme of the present invention, to be intended to comprise within the scope of the claims.
Claims (14)
1. for the synthesis of the method for formula I compound or its steric isomer, described method is included in the reaction between soccerballene and formula II compound:
Wherein
X is C
nh
2n+1,
R is C
nh
2n+1, and
n?=?0-20；
Wherein said soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90;
The molar ratio range that wherein said soccerballene and formula II compound exist in reaction is 1:2 to 2:1; With
Wherein said reaction produces the formula I compound of at least 40% productive rate.
2. the process of claim 1 wherein that the mol ratio that described soccerballene and formula II compound exist in described reaction is 1:1.
3. the process of claim 1 wherein that described reaction also produces the by product that is no more than 22% productive rate.
4. the process of claim 1 wherein that described reaction is by having pk
athe alkaline reagents of >10 causes.
5. the method for claim 4, wherein said alkaline reagents is sodium methylate.
6. the method for claim 1, described method also comprises purge process.
7. the method for claim 6, wherein said purge process is to be selected from one or more in affinity chromatography, reverse-phase chromatography and adsorption chromatography.
8. for the synthesis of the method for formula I compound or its steric isomer, described method comprises the first reaction and the second reaction:
Wherein
X is C
nh
2n+1, and
n?=?0-20；
Described the first reaction comprises alkaline reagents and formula II compound with generation diazoalkane;
Wherein
R is C
nh
2n+1, and
n?=?0-20；
Described the second reaction comprises the diazoalkane producing from described the first reaction is mixed with soccerballene;
Wherein said soccerballene is selected from C
60, C
70, C
76, C
78, C
84and C
90;
The molar ratio range that its Chinese style II compound and described alkaline reagents exist in described the first reaction is 1:2 to 2:1; With
Wherein said the first reaction and described the second reaction produce the formula I compound of at least 40% productive rate.
9. the method for claim 8, the mol ratio that its Chinese style II compound and described alkaline reagents exist in described the first reaction is 1:1.
10. the method for claim 8, wherein said the first reaction and the second reaction generation are no more than the by product of 22% productive rate.
The method of 11. claims 8, wherein said alkaline reagents has pk
a>10.
The method of 12. claims 8, wherein said alkaline reagents is sodium methylate.
The method of 13. claims 8, it also comprises purge process.
The method of 14. claims 13, wherein said purge process is to be selected from one or more in affinity chromatography, reverse-phase chromatography and adsorption chromatography.
Applications Claiming Priority (2)
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|---|---|---|---|
| US13/601,371 | 2012-08-31 | ||
| US13/601,371 US8779207B2 (en) | 2012-08-31 | 2012-08-31 | Method for synthesis of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and fullerene derivatives |
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|---|---|
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| CN106800511A (en) * | 2016-12-14 | 2017-06-06 | 中节能万润股份有限公司 | A kind of fullerene derivate and its application in perovskite solar cell |
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|---|---|---|---|---|
| BR112017008501A2 (en) * | 2014-11-19 | 2017-12-26 | Merck Patent Gmbh | semiconductor mixtures |
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| RU2711566C2 (en) * | 2016-12-28 | 2020-01-17 | Общество с ограниченной ответственностью "ФУНКЦИОНАЛЬНЫЕ ОРГАНИЧЕСКИЕ МАТЕРИАЛЫ" (ООО "ФОМ") | Method of producing cyclopropane fullerene derivatives |
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| US20110130588A1 (en) * | 2008-07-24 | 2011-06-02 | Sumitomo Chemical Company, Limited | Composition, and organic photoelectric conversion element comprising same |
| CN102510851A (en) * | 2009-07-24 | 2012-06-20 | 地方独立行政法人大阪市立工业研究所 | Methanofullerene derivatives and photoelectric conversion elements using same |
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- 2012-08-31 US US13/601,371 patent/US8779207B2/en not_active Expired - Fee Related
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| US20110130588A1 (en) * | 2008-07-24 | 2011-06-02 | Sumitomo Chemical Company, Limited | Composition, and organic photoelectric conversion element comprising same |
| CN102510851A (en) * | 2009-07-24 | 2012-06-20 | 地方独立行政法人大阪市立工业研究所 | Methanofullerene derivatives and photoelectric conversion elements using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106800511A (en) * | 2016-12-14 | 2017-06-06 | 中节能万润股份有限公司 | A kind of fullerene derivate and its application in perovskite solar cell |
| CN106800511B (en) * | 2016-12-14 | 2020-01-31 | 中节能万润股份有限公司 | fullerene derivatives and application thereof in perovskite solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| US20140066647A1 (en) | 2014-03-06 |
| US8779207B2 (en) | 2014-07-15 |
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